Light-sensitive diazotype copying material

ABSTRACT

A diazotype copying material having a light-sensitive coating containing a diazonium salt selected from the group consisting of 2,5-disubstituted derivatives of 4-dibenzylamino-benzene diazonium salt exhibits a very high sensitivity to light.

te States Patent Saito et al.

[ Oct. 30, 1973 LIGHT-SENSITIVE DIAZOTYPE COPYING MATERIAL Related US.Application Data Continuation-impart of Ser. No. 659,609, Aug. 10, 1967,abandoned.

[30} Foreign Application Priority Data Aug. 26, 1966 Japan 41/55819 Nov.29, 1966 Japan.... 41/77761 Nov. 29. 1966 Japan 41/77762 [52] US. Cl.96/91 R, 260/141, 96/49 [51] Int. Cl G03c 1/54 [58] Field of Search96/91.75, 49; 260/141, 142

[56] References Cited UNITED STATES PATENTS 3,272,630 9/1966 Rauhut eta1. 96/91 X 3,379,531 4/1968 Mizianty et a1. 96/91 3,432,301 3/1969Rauhut et a1. 96/91 3,281,246 10/1966 Rauhut et al.. 96/91 3462,27]8/1969 Rauhut et a1. 96/91 59,551 8/1969 Rauhut et a1. 96/91 42,6525/1969 Hectors et al. 96/91 FOREIGN PATENTS OR APPLICATIONS 957,8385/1964 Great Britain 96/91 R 919,037 2/1958 Great Britain 96/91 R867,630 5/1961 Great Britain 915/91 R 1,110,835 4/1968 Great Britain260/141 OTHER PUBLICATIONS Reproduction Paper News Bulletin, AndrewPaper & Chem. Co. Inc. No. 26, Sept. 1960.

Landau, R., Fascicules 1a8 (Les diazo), Distributed by Andrews Papers &Chem. Co. Inc., 1960, p. 30 relied on.

Primary Examiner-Charles L. Bowers, Jr. Attorney-Woodhams, Blanchard &Flynn [57] ABSTRACT A diazotype copying material having alight-sensitive coating containing a diazonium salt selected from thegroup consisting of 2,5-disubstituted derivatives of 4-dibenzylamino-benzene diazonium salt exhibits a very high sensitivity tolight.

1 Claim, No Drawings LIGHT-SENSITIVE DIAZOTYPE COPYING MATERIALCROSS-REFERENCE TO RELATED APPLICATION This application is acontinuation-in-part of our copending application Ser. No. 659 609,filed Aug. 10, 1967, now abandoned.

BAOKGROUND OF THE INVENTION FIELD OF THE INVENTION DESCRIPTION OF THEPRIOR ART In the field of copying techniques which utilize diazoniumcompounds, there has been a demand, since the time such techniques werefound, for copying materials high in light-sensitivity or, in otherwords, a demand for diazonium compounds having high sensitivity tolight. This demand has been on the increase of late, because fluorescentlamps which are not only less expensive but also smaller in the totalradiation energy than mercury lamps have become utilized widely as thelight source for diazotype copying. In order to meet this increasingdemand, there have been introduced various kinds of derivatives ofp-aminobenzene diazonium compounds having relatively high sensitivity tolight.

SUMMARY OF THE INVENTION OIJR wherein:

R is selected from the group consisting of a hydroxyl radical, an alkoxyor phenyl-substituted alkoxy radical having from one to four carbonatoms in the alkyl chain, a morpholino radical, a pyrrolidino radical, apiperidino radical, a piperazino radical and wherein R, and R are alkylradicals having from one to four carbon atoms;

Y is selected from the group consisting of hydrogen, an alkyl radicalhaving from one to four carbon atoms, an alkoxy radical having from oneto four carbon atoms, a hydroxyl-substituted alkoxy radical having fromone to four carbon atoms, and a morpholino-, pyrrolidino-, piperidinoorpiperazino-substituted alkoxy radical having from one to four carbonatoms;

n is an integer between 1 and 4; and

X represents an anionic radical.

The diazonium compounds according to the present invention may beapplied to one-component copying materials which are developed accordingto the moistdevelopment method, two-component copying materials whichare developed according to the drydevelopment method and also tothree-component copying materials which are developed according to thethermal development method. By the use of these diazonium compounds ofthe present invention, there are obtained copies of images varying incolor such as black and blue, depending on the type of the azo couplingcomponent used. According to the present invention, the light-sensitivecopying layer is coated on a support such as paper, precoated paper andplastic foil which is used in ordinary diazotype copying materials. Thiscopying layer may contain an additive such as an anti-yellowing agentand a stabilizer.

The diazonium compounds used in the present invention are prepared, inmany cases, in the form of diazonium chloride or double salt ofdiazonium chloride and metal chloride, and in particular, they areobtained in the form of double salts of diazonium chloride and zincchloride or double salts of diazonium chloride and cadmium chloride. Inthe present invention, however, the type of anion which is coupled tothe diazonium cation is not critical. Diazonium compounds in the formof, for example, bromides, sulfates and fluoroborates may also be usedin the present invention.

With respect to the general formula of the diazonium compounds of thepresent invention, the preferred alkyl radicals include methyl, ethyl,n-propyl, isopropyl, n-butyl and tert-butyl. The preferred alkoxyradicals include methoxy, ethoxy, n-propoxy, iso-propoxy and n-butoxy.The preferred N R2 radicals include N-methylamino, N-ethylamino, N,N-dimethylamino, N,N-diethylamino and, N,N-npropylamino.

As has been stated, the diazonium compounds of the present invention maybe applied to one-component, two-component and three-component copyingmaterials. The diazonium compounds show an increased coupling velocityand such compounds are particularly suitable for both one-component andtwo-component copying materials.

Hereunder are enumerated typical diazonium compounds which are used inthe present invention. It should be understood, however, that thediazonium compounds which are usable in the present invention are notrestricted to these compounds alone.

Formula 1 Formula 2 h C 1H4 O H2- Formula 3 Formula 4 Formula 5 CH3 igag O C2H4N (C2115) HCl (124-129 C.) [4l0-415 m (l28-132 c.) 410 115 mu](105-111 C.) [410-415 mp] (119-122 C.) [400-405 mp] NOTE: (Decompositionpoint), [ultraviolet absorption].

FORMULA l Seventy grams of S-(B-hydroxy) ethoxyaniline and 82 g ofsodium acetate were dissolved in 50 ml of water. While holding thetemperature of this solution between 90C. and 100C, 127 g of benzylchloride were added, in drops, to the solution while stirring. After themixture was left to react for about five hours, the supernatant oillayer was removed and distilled under a reduced pressure of 1 mmHg. As aresult, g of distillate boiling between 240C. and 255C. were obtained(This substance had a melting point between 665C. and 67.5C.). Thisdistillate was coupled to a diazonium compound of p-nitroaniline toproduce a dyestuff, with the yield being 57 g (The resulting substancehas a melting point between 202C. and 204C). This dyestuff was thenreduced with hydrogen gas to an amino compound. This latter compound wasreacted with acetic anhydride to cause N,N-diacetyl-pdiaminobenzene toseparate out. The obtained acetyl compound was subjected to hydrolysis,followed by diazotization in a known manner. The resulting diazoniumcompound was salted out with zinc chloride. Thus 15 g of4-dibenzylamino-5-(B-hydroxy) ethoxy benzene diazonium chloride, zincchloride double salt which was yellow in color were obtained. Thisdouble salt had a decomposition point between 123C. and 125C, and had apeak ofultraviolet absorption at 410 FORMULA 2 One hundred twenty-onegrams of S-(B-benzyloxy) ethoxy aniline and 82 g of sodium acetate weredissolved in 50 ml of water. While holding the temperature of thissolution between C. and C., 127 g of benzyl chloride were added, indrops, to the solution while stirring. After the mixture was left toreact for about six hours, the supernatant oil layer was removed anddissolved in 400 ml of toluene. The resulting solution was subjected towashing with water two or three times and to dehydration with anhydroussodium sulfate. Then, hydrogen chloride gas was introduced into thesolution, 1 15 g of chloride were separated from the solution (Thischloride had a melting point between 210C. and 212C). This chloride wasdissolved in acetic acid and coupled, in the presence of sodiumchloride, to a diazonium compound of p-nitroaniline. The

resulting coupled compound was neutralized with additional sodiumacetate, thereby producing a dyestuff, with the yield being 106 g (Theresulting substance had a melting point between 210C. and 212C.). Thisdyestuff was then reduced with hydrogen gas to an amino compound. Thislatter compound was reacted with acetic anhydride to causeN,N-diacetyl-pdiaminobenzene to separate out. The obtained acetylcompound was subjected to hydrolysis, followed by diazotization by knownmanner, and salted out by zinc chloride. Thus 18 g of4-dibenzylamino-5-(B-benzyloxy)ethoxybenzene diazonium chloride, zincechloride double salt which was yellow in color were obtained. Thisdouble salt had a decomposition point between 99C. and 102C. and a peakof ultraviolet absorption within the range of from 405 mu to 410 mu.

FORMULA 4 Eighty-two grams of 2-methyl-5-(B-hydroxy) ethoxyaniline and82 g of sodium acetate were dissolved in 50 ml of water. While holdingthe temperature of this solution between 90C. and 100C., 127 g of benzylchloride were added, in drops, to the solution while stirring. After themixture was left to react for about 7 hours, the supernatant oil layerwas removed and distilled under a reduced pressure of 1 mmHg. As aresult, 98 g of distillate boiling between 243C. and 248C. wereobtained. This distillate was coupled to a diazonium compound ofp-nitroaniline to produce a dyestuff, with the yield being 68 g (Theresulting substance had a melting point between 197C. and 199C) Thisdyestuff was then reduced with hydrogen gas to an amino compound. Thislatter compound was reacted with acetic anhydride to causeN,N'-diacetyl-pdiaminobenzene to separate out. The obtained acetylcompound was subjected to hydrolysis, followed by diazotization by knownmanner, and was salted out by zinc chloride. Thus 18 g of4-dibenzylamino-2-methyl- S-(B-hydroxy) ethoxybenzene diazoniumchloride, zinc chloride double salt which was yellow in color wereobtained. This double salt had a decomposition point between 124 C. and129C., and had a peak of ultraviolet absorption within the range of from410 my. to 415 mu.

FORMULA 5 One hundred and five grams of 2-methyl-5-(B- pyrrolidino)ethoxyaniline and 82 g of sodium acetate were dissolved in 50 ml ofwater. While maintaining the temperature of this solution between 90C.and 100C.,

127 g of benzyl chloride were added, in drops, to the solution whilestirring. After the mixture was left to react for about six hours, thesupernatant oil layer was removed and dissolved in 400 ml of toluene.The resulting solution was subjected to washing with water two or threetimes and to dehydration with anhydrous sodium sulfate. Then, hydrogenchloride gas was introduced into the solution and 1 12 g of chloridewere separated from the solution (This substance had a melting pointbetween 178C. and 182C) This chloride was dissolved in acetic acid andcoupled, in the presence of sodium chloride, with a diazonium compoundof pnitroaniline to produce a dyestuff, with the yield being 105 g (Theresulting substance had a melting point between 207C. and 209C.). Thisdyestuff was then reduced with hydrogen gas to an amino compound. Thislatter compound was reacted with acetic anhydride to causeN,N'-diacetyl-p-diaminobenzene to separate out.

The obtained acetyl compound was subjected to hydrolysis, followed bydiazotization by known manner, and salted out by zinc chloride. Thus 28g of 4- dibenzylamino-2-methyl-5-(B-pyrrolidino) ethoxybenzene diazoniumchloride, zinc chloride double salt which was yellow in color wereobtained. This double salt has a decomposition point between 128C. and132C. and a peak of ultraviolet absorption within the range of 410 mg to415 mu.

FORMULA 8 One hundred eleven grams of Z-methyl-S-(B- morpholino)ethoxyaniline and 82 g of sodium acetate were dissolved in 50 ml ofwater. While maintaining the temperature of this solution between C. andC., 127 g of benzyl chloride were added, in drops, to the solution whilestirring. After the mixture was left to react for about six hours, thesupernatant oil layer was removed and dissolved in 400 ml of toluene.The resulting solution was subjected to washing with water two or threetimes and to dehydration with anhydrous sodium sulfate. Then, hydrogenchloride gas was introduced into the solution and 121 g of chloride wereseparated from the solution (This substance had a melting point between185C. and 187C) This chloride was dissolved in acetic acid and coupled,in the presence of sodium acetate, with a diazonium compound ofpnitroaniline to produce a dyestuff, with the yield being 1 12 g (Theresulting substance had a melting point between 215C. and 218C.). Thisdyestuff was then reduced with hydrogen gas to an amino compound. Thislatter compound was reacted with acetic anhydride to causeN,N-diacetyl-p-diaminobenzene to separate out. The obtained acetylcompound was subjected to hydrolysis, followed by diazotization by knownmanner, and salted out by zinc chloride. Thus 28 g of 4-dibenzylamino-2-methyl-5-(,B-morpholino) ethoxybenzene diazoniumchloride, zinc chloride double salt which was yellow in color wereobtained. This double salt had a decomposition point between 118C. and120C. and a peak of ultraviolet absorption within the range of 400 my.to 405 my" FORMULA 10 One hundred grams of 2,5-(B-hydroxy) ethoxyanilineand 82 g of sodium acetate were dissolved in 50 ml of water. Whileholding the temperature of this solution between 90C. and 100C., 127 gof benzyl chloride were added, in drops, to the solution while stirring.After the mixture was left to react for about 5 hours, the supernatantoil layer was removed and distilled under a reduced pressure of 1 mmHg.As a result, 95 g of distillate boiling between 257C. and 261C. wereobtained. This distillate was coupled to a diazonium compound ofp-nitroaniline to produce a dyestuff, with the yield being 75 g (Theresulting substance had a melting point between 208C. and 210C.). Thisdyestuff was then reduced with hydrogen gas to an amino compound. Thislatter compound was reacted with acetic anhydride to causeN,N-diacetyl-pdiaminobenzene to separate out. The obtained acetylcompound was subjected to hydrolysis, followed by diazotization by knownmatter, and salted out by zinc chloride. Thus 32 g of4'-dibenzylamin0-2,5-(B- hydroxy) ethoxybenzene diazonium chloride, zincchloride double salt which was yellow in color were obtained. Thisdouble salt had a decomposition point between l30C.'and 136C., and had apeak of ultraviolet absorption within the range offrom 405 mu to 410 mu.

FORMULA ll One hundred seventy-six grams of 2,5-di(;8- morpholino)ethoxyaniline and 82 g of sodium acetate were dissolved in 50 ml ofwater. While maintaining the temperature of this solution between 90C.and 100C., 127 g of benzyl chloride were added, in drops, to thesolution while stirring. After the mixture was left to react for aboutsix hours, the supernatant oil layer was removed and dissolved in 400 mlof toluene. The resulting solution was subjected to washing with watertwo or three times and to dehydration with anhydrous sodium sulfate.Then, hydrogen chloride gas was introduced into the solution and 131 gof chloride were separated from the solution (This substance had amelting point between 217C. and 219C). This chloride was dissolved inacetic acid and coupled, in the presence of sodium chloride, to adiazonium compound of pnitroaniline. The resulting coupled compound wasneutralized with sodium acetate, thereby producing a dyestuff, with theyield being 125 g (The resulting substance had a melting point between231C. and 233C This dyestuff was then reduced with hydrogen gas to anamino compound. This latter compound was reacted with acetic anhydrideto cause N,N'-diacetyl-pdiaminobenzene to separate out. The obtainedacetyl compound was subjected to hydrolysis, followed by diazotizationby known manner, and salted out by zinc chloride. Thus 51 g of4-dibenzylamino-2,5-(B- morpholino) ethoxybenzene diazonium chloride,zinc chloride double salt which was yellow in color were obtained. Thisdouble salt had a decomposition point between 135C. and 140C. and a peakof ultraviolet absorption within the range of 405 my. to 410 my"DESCRIPTION OF THE PREFERRED EMBODIMENTS I EXAMPLE l A white support foruse in diazotype copying materials was precoated with an emulsionconsisting of finely granular silica and vinyl acetate. Onto thisprecoated support was applied a solution having the followingcomposition:

4-dibenzylamino-5-(B-hydroxy) ethoxy benzene diazonium chloride, zincchloride double salt (refer to Formula 1) 1.3 g

Tartaric acid 0.4 g

Boric acid 0.1 g

Water 100 ml andthe sheet was dried.

An original was placed on the light'sensitive copying layer thusobtained and was exposed to light by the use of an illuminatingapparatus employing a fluorescent lamp to form a latent image on thelayer. This exposure was completed in a very short length of time. Thecopying layer carrying the latent image was developed in a solutionhaving the following composition:

Thiourea 1.5 g

Phloroglucin 0.4 g

Benzoic acid 0.25 g

Sodium benzoate 1.5 g Sodium phosphate 1.5 g Water ml The developingsolution had a pH of about 5.9. The development was carried out rapidly,and the obtained copy had an image of black in color. The half toneareas of the image obtained were consistent in color with the maximumdensity areas of this reproduced im age.

EXAMPLE-2 A support for use in ordinary diazotype lightscnsitive copyingmaterials was coated with a sensitizing solution of the followingcomposition:

4-dibenzylamino-2,S-(B-hydroxy) ethoxybenzene diazonium chloride, zincchloride double salt (Refer to Formula 10) 1.5 g

Tartaric acid 6.0 g

Boric acid 1.0 g

Acetic acid 2.0 g

Water 100.0 g

Caffeine 0.5 g

Methyl cellulose 0.08 g

lso-propanol 3.0 g

2-hydroxy naphthalene-3-carboxylic acid-di-(Z'-hydroxyethyl) amide 3.0 gand the paper was dried. The coated layer was exposed to light in amanner similar to that described in Example l and the resulting layerwas brought into contact with an ammonia gas having a high ammoniaconcentration to develop the image. The developed copy showed a deepblue image.

In case the development was performed by the use of an alkaline aqueoussolution composed of:

Potassium metaborate 3 g Potassium carbonate 2 g Water 100 g in lieu ofthe aforementioned ammonia gas, a similar, satisfactory copy wasobtained.

EXAMPLE 3 A solution consisting of:

Ethyleneglycol monomethylether 20 Formic acid 3 g Water 35 gIso-propanol 40 g Citric acid 3 g Cresyl glutaric acid 2 g4-dibenzylamino-2-methyl-S-(B-ethoxy) ethoxy benzene diazonium compound,zinc chloride double salt (Refer to Formula 6) 4 g was applied to anacetyl cellulose sheet and was dried. Development was conducted with anammonia gas in a manner similar to that of Example 2, and a copy yellowin color was obtained. This copy could be used as a good intermediateoriginal since it has a property to intensively absorb ultraviolet raysand the rays locating in the regions near thereof.

We claim:

1. A light-sensitive copying material for the diazotype processcomprising a support and a photosensitive layer coated on said support,said layer comprising a diazonium compound having the formula:

\N Nix or? Q a (01mm 5 wherein:

R is selected from the group consisting of hydroxyl, alkoxy having fromone to four carbon atoms, a group of the formula in which R, is alkylenehaving from one to four car- 5 bon atoms, aryloxy,

N and n is an integer between one and four; and

X represents an anionic radical.

